Compositions of and methods for using hydraulic fracturing fluid for petroleum production

ABSTRACT

A hydraulic fracturing fluid for use in oilfield applications is disclosed, the hydraulic fracturing fluid includes a spherical bead-forming liquid composition, the spherical bead-forming liquid composition comprised of a primary liquid precursor and a secondary liquid precursor, the primary liquid precursor comprises a micellar forming surfactant, a bead-forming compound, and a non-solids bearing liquid solvent; and the secondary liquid precursor comprises one or more curing agents, and one or more co-curing agents.

PRIORITY CLAIM

This application is a non-provisional application claiming priority toU.S. Prov. App. No. 62/081,617, filed Nov. 19, 2014, the entiredisclosure of which is expressly incorporated by reference.

TECHNICAL FIELD

The present disclosure relates to a hydraulic fracturing fluid for oilfield applications. More specifically, the present disclosure relates toa hydraulic fracturing fluid containing a spherical bead-forming liquidcomposition for forming in-situ spherical beads for improved oil and gasrecovery.

BACKGROUND

Hydraulic fracturing is a process used to increase the permeability of ahydrocarbon-bearing reservoir in order to increase the flow of oil andgas to the surface. While effective, hydraulic fracturing operations areresource intensive. For example, for hydraulic fracturing operations ina shale gas reservoir, each well requires an average of 400 tankertrucks to carry water and supplies to and from the fracturing site;requiring at times 8 million gallons of water to complete eachfracturing stage, with each well requiring multiple fracturing stages.The water is mixed with sand and chemicals to create the fracturingfluid. In addition, approximately 40,000 gallons of chemicals are usedper fracturing job. By some estimates, there are 500,000 active gaswells in the United States requiring approximately 72 trillion gallonsof water. The source of water, the leak off of the fracturing water intothe reservoir, and the treatment of recovered water have become seriousissues with economic and environmental concerns.

One of the components in a hydraulic fracturing fluid is the proppantcomponent. Proppants are used in the fracturing process to keepfractures open and permeable to the flow of hydrocarbons, including oiland gas, after the external pressure of the hydraulic fracturing fluidis withdrawn. Traditional proppants include solids comprising one ormore of sand, geopolymers, ceramics, resin coated sand, and glass beads.The hydraulic fracturing fluid used to carry and place the proppant inthe fracture generally contains water, polymer, crosslinker, fluid lossadditives, flow back additives, surfactants, clay stabilizers, proppant,and gel breaker. The polymer is used to provide viscosity and keep theproppants suspended until they have reached their desired location inthe fracture. The breakers are used to reduce the polymer viscosity,allowing the particles to settle and the liquid portion of thefracturing fluid to be returned to the surface when the externalpressure is removed and the overburden pressure partially closes thefracture. The proppants remain in the fracture and form permeabilitychannels to increase the oil or gas production.

SUMMARY

The present disclosure relates to compositions and methods forfracturing a reservoir. More specifically, the disclosure relates tocompositions and methods for fracturing a reservoir and in-situ proppantgeneration using polymeric materials. In some embodiments, an injectedhydraulic fracturing fluid is converted into a highly permeable proppantpack in-situ. Since the fracturing fluid itself forms the proppant, itcan penetrate the entire fracture length and height within a complexfracture network, maximizing the effective fracture area and stimulatedreservoir volume. The rendered particle sizes can be significantlylarger than conventional proppants without the concern of screen-out.The in-situ formed proppants have strength sufficient to resist fractureclosure stress. In some embodiments, no polymer is required to suspendthe proppant; therefore no gel residue is left to damage fractureconductivity.

The present disclosure provides a hydraulic fracturing fluid for use inoilfield applications, and the hydraulic fracturing fluid includes aspherical bead-forming liquid composition. The spherical bead-formingliquid composition is comprised of a primary liquid precursor and asecondary liquid precursor. The primary liquid precursor includes amicellar forming surfactant, a bead-forming compound, and a non-solidsbearing liquid solvent. The secondary liquid precursor comprises acuring agent, and a co-curing agent.

In some embodiments, the primary liquid precursor further comprises ananti-foaming agent. In other embodiments, the primary liquid precursorfurther comprises a pH control agent. Still in other embodiments, themicellar forming surfactant is selected from the group consisting ofanionic surfactants, cationic surfactants, nonionic surfactants,amphoteric surfactants and combinations thereof. In some embodiments,the bead-forming compound is selected from the group consisting ofbis-phenol A, bis-phenol F, cycloaliphatic epoxides, glycidyl ethers,poly glycidyl ethers, novalac resins, polyurethane resins, acrylicresin, phenol-formaldehyde resin, epoxy functional resins, andcombinations thereof.

Still in other embodiments, the non-solids bearing liquid solvent isselected from the group consisting of water, brine containing mono andpolyvalent salt, sea water, mineral oil, kerosene, diesel, crude oil,and petroleum condensate, low molecular weight alcohols, low molecularweight alcohol ethers, benzyl alcohol, and benzyl alcohol ethers, ethylcarbitol ether, γ-butyrolactone, phenol alkoxylates, alkylphenolalkoxylates, and combinations thereof.

In certain embodiments, the pH control agent is selected from the groupconsisting of hydrochloric acid, sulfuric acid, phosphoric acid, sodiumhydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,potassium phosphate, sodium silicate, potassium silicate, organic acids,and combinations thereof. In some embodiments, the curing agent isselected from the group consisting of lewis acids, tertiary amines, monoethanol amine, benzyl dimethylamine, 1,4-diaza-bicylo[2,2,2]octane,1,8-diazabicylo[5,4,0]undec-7ene, cycloaliphatic amines, amidoamines,aliphatic amines, aromatic amines, isophorone, isophorone diamine,polyamides, boron tri-fluoride derivatives, functional resins,imidazoles, imidazolines, mercaptans, sulfide, hydrazides, amides andtheir derivatives.

Still in yet other embodiments, the co-curing agent is selected from thegroup consisting of water, fatty acids, such as oleic acid, tall oilfatty acid, ricinoleic acid, benzoic acid, salicylic acid, stearic acidas well as alkoxylated alcohols, dicarboxylic acids, carboxylic acids,imidazolines, dicyandiamides, ureas, imidazoles, thiols, aliphaticpolyamines, cycloaliphatic polyamides, cycloaliphatic dicarboxylic acidanhydrides, imidazoline salts, dicyandamides, phenols and alkylphenols.

In certain embodiments, the spherical bead-forming liquid composition isa non-solids bearing homogenous liquid. In other embodiments, thespherical bead-forming liquid composition has a liquid viscosity fromabout 20 centipoise (cp) to about 80 cp.

Additionally disclosed is a method of fracturing a reservoir with aspherical bead-forming liquid composition that forms a hydraulicfracturing fluid that generates fractures in the reservoir, and themethod includes the step of mixing a primary liquid precursor and asecondary liquid precursor to form the spherical bead-forming liquidcomposition. The primary liquid precursor includes a micellar formingsurfactant, a bead-forming compound, and a non-solids bearing liquidsolvent. The secondary liquid precursor includes one or more curingagents, and one or more co-curing agents. The method further includesthe steps of pumping the spherical bead-forming liquid composition intoan injection well in the reservoir at an external pressure greater thana pressure to generate fractures in the reservoir; allowing thespherical bead-forming liquid composition to migrate into the fracturesof the reservoir; and allowing the primary liquid precursor andsecondary liquid precursor to react to form in-situ spherical beads, thein-situ spherical beads are operable to keep the fractures open afterthe external pressure is released.

In some embodiments, the method further comprises the step of adding ananti-foaming agent to the primary liquid precursor. In some embodiments,the method further includes the step of adding a pH control agent to theprimary liquid precursor. Still in other embodiments, the micellarforming surfactant is selected from the group consisting of anionicsurfactants, cationic surfactants, nonionic surfactants, amphotericsurfactants and combinations thereof. In other embodiments, thebead-forming compound is selected from the group consisting ofbis-phenol A, bis-phenol F, cycloaliphatic epoxides, glycidyl ethers,poly glycidyl ethers, novalac resins, polyurethane resins, acrylicresin, phenol-formaldehyde resin, epoxy functional resins, andcombinations thereof.

In some embodiments of the method, the non-solids bearing liquid solventis selected from the group consisting of water, brine containing monoand polyvalent salt, sea water, mineral oil, kerosene, diesel, crudeoil, and petroleum condensate, low molecular weight alcohols, lowmolecular weight alcohol ethers, benzyl alcohol, and benzyl alcoholethers, ethyl carbitol ether, γ-butyrolactone, phenol alkoxylates,alkylphenol alkoxylates, and combinations thereof.

Still in other embodiments of the method, the pH control agent isselected from the group consisting of hydrochloric acid, sulfuric acid,phosphoric acid, sodium hydroxide, potassium hydroxide, sodiumcarbonate, potassium carbonate, potassium phosphate, sodium silicate,potassium silicate, organic acids, and combinations thereof. In certainembodiments, the curing agent is selected from the group consisting oflewis acids, tertiary amines, mono ethanol amine, benzyl dimethylamine,1,4-diaza-bicylo[2,2,2]octane, 1,8-diazabicylo[5,4,0]undec-7ene,cycloaliphatic amines, amidoamines, aliphatic amines, aromatic amines,isophorone, isophorone diamine, polyamides, boron tri-fluoridederivatives, functional resins, imidazoles, imidazolines, mercaptans,sulfide, hydrazides, amides and their derivatives.

Still in other embodiments, the co-curing agent is selected from thegroup consisting of fatty acids, such as oleic acid, tall oil fattyacid, ricinoleic acid, benzoic acid, salicylic acid, stearic acid aswell as alkoxylated alcohols, dicarboxylic acids, carboxylic acids,imidazolines, dicyandiamides, ureas, imidazoles, thiols, aliphaticpolyamines, cycloaliphatic polyamides, cycloaliphatic dicarboxylic acidanhydrides, imidazoline salts, dicyandamides, phenols and alkylphenols.

In some embodiments of the method, the spherical bead-forming liquidcomposition is a non-solids bearing homogenous liquid. In someembodiments of the method, the spherical bead-forming liquid compositionhas a liquid viscosity from about 20 centipoise (cp) to about 80 cp.

Various additives may be added to the hydraulic fluid before it isinjected into the reservoir. These include but are not limited to:corrosion inhibitors, scale inhibitors, clay stabilizers, biocides,fluid loss additives, and friction reducers.

BRIEF DESCRIPTION OF THE DRAWINGS

These and other features, aspects, and advantages of the disclosure willbecome better understood with regard to the following descriptions,claims, and accompanying drawings. It is to be noted, however, that thedrawings illustrate only several embodiments of the disclosure and aretherefore not to be considered limiting of the disclosure's scope as itcan admit to other equally effective embodiments.

FIG. 1 is a top view pictorial representation of the progress ofspherical bead formation at time zero, 30 minutes, and 60 minutes.

FIG. 2 is a pictorial representation of the spherical beads formed inExample 1.

FIG. 3 is a pictorial representation of the spherical beads formed inExample 2.

FIG. 4 is a pictorial representation of the spherical beads formed inExample 3.

FIG. 5 is a pictorial representation of the spherical beads formed inExample 4.

FIG. 6 is a graph of the effect of pot-life versus bead size.

FIG. 7 is a pictorial and schematic representation of the estimateddistribution of bead sizes within fractures in a reservoir.

FIG. 8 is a pictorial representation of a comparison of flow of oilthrough a container with sand (right) and a container with sphericalbeads according to an embodiment as disclosed in Example 6 (left).

FIG. 9 is a pictorial representation of a variety of sizes of solidbeads produced under an in-situ temperature of 150° F.

FIG. 10 is a schematic representation of a mechanical load-bearing testperformed on spherical beads produced by embodiments of the presentdisclosure.

FIG. 11 is a graph comparing the mechanical behavior among two in-situproppant formulations of the present disclosure and conventional highstrength bauxite proppant (20/40 HSP) and intermediate strength proppant(16/30 ISP).

FIG. 12 is a pictorial representation of the spherical particles of thein-situ proppant 1 pack from FIG. 11 rebounded to nearly the same shapeas stress is released from the maximum loading of 14,000 pounds persquare inch (psi).

FIG. 13 is a pictorial representation showing grains of the 20/40 HSPfrom FIG. 11 before (left) and after (right) being loaded to 14,000 psi.

FIG. 14 is a pictorial representation of the grains of the 16/30 ISPfrom FIG. 11 before (left) and after (right) being loaded to 14,000 psi.

FIG. 15 is a pictorial representation of grains of 16/20 resin coatedproppant (RCP) before (left) and after (right) being loaded to 14,000psi.

FIG. 16 is a pictorial representation of grains of 20/40 light weightceramic proppant (RCP) before (left) and after (right) being loaded to14,000 psi.

DETAILED DESCRIPTION

While the disclosure will be described in connection with severalembodiments, it will be understood that it is not intended to limit thedisclosure to those embodiments. On the contrary, it is intended tocover all the alternatives, modifications, and equivalents as may beincluded within the spirit and scope of the disclosure defined by theappended claims.

The present disclosure describes a hydraulic fracturing fluid thatincludes a spherical bead-forming liquid composition. The hydraulicfracturing fluid is injected into a subterranean reservoir undersufficient external pressure generating fractures in the reservoir. Thehydraulic fracturing fluid is allowed to migrate into the fractures inthe reservoir. The spherical bead-forming liquid composition reactsin-situ to form in-situ spherical beads. The in-situ spherical beads actas proppants in the fractures in the reservoir to prevent the fracturesfrom closing when the external pressure is removed.

The spherical bead-forming liquid composition is composed of a mixtureof a primary liquid precursor and a secondary liquid precursor. Themixture of the primary liquid precursor and the secondary liquidprecursor are mixed to form a spherical bead-forming liquid composition.

In certain embodiments, the hydraulic fracturing fluid is a non-solidscontaining hydraulic fluid containing liquid proppant precursors, andthis provides many advantages over conventional formulations andprocesses. Minimal abrasion on the pumping equipment is experiencedsince no solids are present in the injection fluid as compared toconventional solid-proppant-laden fracturing fluids. The hydraulic fluidcan more effectively penetrate deeply into the formation through complexfracture networks, forming in-situ proppants to allow entire inducedfractures to contribute to oil and gas production. The absence of solidsalso eliminates the possibility of bridging at the head ofmicrofractures and convoluting pathways within the hydrocarbon-bearingformation that would prevent further penetration of the hydraulic fluid.

The in-situ formed spherical beads can be significantly larger thanconventional proppants. This allows enhancement of fractureconductivity. In carbonate reservoirs, the in-situ proppants caneffectively overcome the short etching pattern suffered during acidfracturing for rapid acid spending rate; they also eliminate the concernof corrosion caused by a large volume of acid injection.

The formed beads exhibit elastic mechanical behavior under loads so theproppant flow back can be effectively controlled. The stiffness of thein-situ set proppants increases as the closure stress increases. Thebeads remain elastic, and therefore no crushing is experienced, as thereis by conventional brittle proppants, which generate fines (shown inFIGS. 14-16). Without being bound by any theory or explanation, thisunique characteristic is one believed to help sustain the fractures overlong durations.

The primary liquid precursor includes one or more micellar formingsurfactants, one or more primary bead-forming compounds, and one or moreliquid non-solids bearing solvents (also called liquid solvent carrier).The primary liquid precursor optionally includes one or moreanti-foaming agents, optionally one or more pH control agents, andoptionally one or more retarders.

The components of the primary liquid precursor are chosen to becompatible in the primary liquid precursor and to be capable forcreating an environment from which the in-situ spherical beads can form.

Any micellar forming surfactant that can alter the wettability of thein-situ spherical beads can be used. The wettability of the in-situspherical beads can be varied from water wet, oil wet or partiallyoil/water wet by the micellar forming surfactant. Exemplary micellarforming surfactants include anionic surfactant, cationic surfactant,nonionic surfactant, and amphoteric surfactant.

Exemplary bead-forming compounds include bis-phenol A, bis-phenol F,Epon® 828, Epon® 871, Degussa F126®, cylcloaliphatic epoxides, glycidylethers, poly glycidyl ethers, Cardolite NC 547® , DER 732®, DER 736®,MAX CLR™ A, novalac resins, polyurethane resins, acrylic resin,phenol-formaldehyde resin, and epoxy functional resins.

Exemplary liquid non-solids bearing solvents include aqueous solventsand non-aqueous solvents. Exemplary aqueous solvents include water,water containing one or more of mono and polyvalent cation salts,seawater, produced brine, and synthetic brine. Exemplary non-aqueoussolvents include mineral oil, kerosene, diesel, crude oil, petroleumcondensate, alcohols, low molecular weight alcohols, esters, lowmolecular weight alcohol ethers, benzyl alcohol, and benzyl alcoholethers, ethyl carbitol ether, γ-butyrolactone, phenol alkoxylates,alkylphenol alkoxylates, fatty acids and combinations thereof. Lowmolecular weight alcohols as used throughout the disclosure refer tothose alcohols containing a linear, branched, saturated or unsaturatedprimary carbon chain containing from one to eight carbons. Exemplaryalcohols include methanol, ethanol, n-propanol, iso-propanol, butanol,iso-butanol, 2-ethyl hexanol, cyclohexanol, benzyl alcohol and like.Exemplary ethers include but are not limited to ethylene glycolmonobutyl ether, alkoxylated benzyl alcohol, alkoxylated hexanol, andalkoxylated butanol. In at least one embodiment of the presentdisclosure, the liquid non-solids bearing solvent is an organic solvent.In at least one embodiment of the disclosure, the liquid non-solidsbearing solvent is incorporated into the matrix of the in-situ sphericalbead.

The antifoaming agent may be any of a number of products that have beenfound to reduce foam during downhole applications, including siliconeand non-silicone antifoams.

Exemplary pH control agents include hydrochloric acid, hydrofluoricacid, sulfuric acid, phosphoric acid, sodium hydroxide, sodiumaluminate, potassium hydroxide, sodium carbonate, potassium carbonate,potassium phosphate, sodium silicate, potassium silicate and organicacids or bases.

Exemplary retarders include tertiary amines, diluents, metal complexes,one or more of mono and polyvalent alkali salts, and may be added as isknown in the art.

The secondary liquid precursor includes one or more curing agents. Thesecondary liquid precursor optionally includes one or more co-curingagents, and optionally one or more retarders.

Exemplary curing agents include lewis acids, tertiary amines, monoethanol amine, benzyl dimethylamine, 1,4-diaza-bicylo[2,2,2]octane,1,8-diazabicylo[5,4,0]undec-7ene, cycloaliphatic amines, amidoamines,aliphatic amines, aromatic amines, isophorone, isophorone diamine,polyamides, boron tri-fluoride derivatives, functional resins,imidazoles, imidazolines, mercaptans, sulfide, hydrazides, amides andtheir derivatives.

Exemplary co-curing agents include water, fatty acids, such as oleicacid, tall oil fatty acid, ricinoleic acid, benzoic acid, salicylicacid, stearic acid as well as alkoxylated alcohols, dicarboxylic acids,carboxylic acids, imidazolines, dicyandiamides, ureas, imidazoles,thiols, aliphatic polyamines. cycloaliphatic polyamides, cycloaliphaticdicarboxylic acid anhydrides, imidazoline salts, dicyandiamides, phenolsand alkylphenols.

The spherical bead-forming liquid composition may optionally includeliquid soluble cross linker, initiator, or diluents.

In some embodiments, the spherical bead-forming liquid composition is ahomogenous liquid. In some embodiments, the liquid composition has aliquid viscosity from about 20 centipoise (cp) to about 80 cp, or fromabout 30 cp to about 60 cp, or about 40 cp to about 50 cp, or about 40cp. The viscosity can be adjusted by mixing the precursors in differentbase fluids, such as, for example, one or more of brine, seawater, oil,and other organic liquids. The density of the liquid mixture is also afunction of the base fluid. The viscous liquid serves as the fracturingfluid as well as proppants once it enters the fracture and becomesstatic. The extent of mixing of the formulation and its residence timeas it propagates through the fracture results in the formation ofspherical beads.

In a method of using the spherical bead-forming liquid composition, thehydraulic fracturing fluid of the present disclosure is pumped into thereservoir at an external pressure. The external pressure is greater thanthe pressure needed to fracture the reservoir. The hydraulic fracturingfluid of the present disclosure is pumped into the well where thecomponents in the primary liquid precursor and the components in thesecondary liquid precursor are allowed to react and form in-situspherical beads. The in-situ spherical beads serve as proppants, watershut off agents, permeability modifiers, or sand control agents. In atleast one embodiment, where the in-situ spherical beads act aspermeability modifiers, the in-situ spherical beads form in thefractures generated by pumping in the hydraulic fracturing fluid andhold open the fractures against the overburden pressure. After thehydraulic fracturing fluid is no longer pumped into the reservoir, thepressure in the wellbore is reduced. The in-situ spherical beads preventthe fractures from closing and allow hydrocarbons to flow from thereservoir to the wellbore.

In some embodiments, the fracturing fluid is solids free and containschemical precursors that will set into spherical particle beads deepwithin the reservoir to serve as proppants which keep the flow channelsopen and allow oil and gas to be easily transported into a well. Thein-situ formed propping agent can be significantly larger thanconventional proppants without screening out effects. The largerproppant also creates much higher fracture conductivity. The size of thespherical beads is controlled, in part, by the precursors and theirresidence time within the fractures. Longer pumping times and longersetting times will result in smaller spherical beads, which can supportthe micro-fractures further from the wellbore. Larger spherical beadswill form and remain in the main fracture and near the wellbore. Most ofthe precursors present in the injected fracturing fluid will be consumedwhile setting into the beads, and therefore there is very little fluidto flow back to a well. This can significantly reduce the time for theonset of production from a well.

Another feature of in-situ proppants of the present disclosure is thatembodiments can be formulated into a fluid system that is basicallywater free by choosing an organic solvent such as one or more of crudeoil, alcohols, esters, and fatty acids for main components to be mixedin. Within the hydrocarbon-bearing formation, clay swelling and finesmigration issues can be minimized. In regions that fresh wateravailability is limited, such as offshore environments, the fluid can bemade up with seawater or high salinity water to relieve the burden onthe environment and transportation logistics.

The extent of mixing of the spherical bead-forming liquid compositionand its residence time as it propagates through the fracture results inthe formation of spherical beads. The diameter and the hardness of thespherical beads can be controlled by the pot life of the primary liquidprecursor and secondary liquid precursor. Pot life refers to the timebetween when the spherical bead-forming liquid composition is pumped(injected) into the reservoir and the point in time at which thespherical bead-forming liquid composition reaches a viscosity at whichthe spherical liquid composition is unpumpable. The components in theprimary liquid precursor and secondary liquid precursor affect the potlife of the spherical bead-forming liquid composition. Small diameterspherical beads are preferred for micro-fractures at the head of thefracture and progressively larger diameter spherical beads within thefracture and closer to the well borehole (see FIG. 7).

The pot life required to commence forming in-situ spherical beads can bevaried by adding retarders and accelerators. Exemplary acceleratorsinclude acids, bases, fatty acids, amines, amides, and alcohols. Thediameter and the hardness of the beads can be controlled by the reactiontime between solid-forming precursors. According to the formationproperties, the fracturing treatment could be designed as such thatsmall diameter beads are formed in the tip of fracture or in narrowfractures and progressively larger diameter beads are formed at the tailof fracture near a wellbore. A viscous pad can be pumped ahead of thein-situ proppant fluid if necessary to create fracture geometry and toprovide leak-off control.

Once placed in the fracture, the liquid mixture in the fracture reactsinternally before the fracture closes to convert into spherical solidbeads, which are mechanically strong enough to keep the fracture open(discussed further as follows in the Examples). Once set, the proppantpack is highly conductive for flow of the reservoir fluid to be producedthrough such high porosity media. FIG. 1 shows an example of the in-situproppant formation process through time at 150° F. In general, the beadscan be formed in less than 15 minutes and up to more than 8 hours afterthe two precursors are mixed. In FIG. 1, the photo on the left shows ahomogeneous liquid containing the precursors of the settable solid. Themiddle photo shows the onset of the solid forming when the fluid was setfor 30 minutes at temperature after mixing. The photo on the right showsthe growth of the beads after sitting stagnant for 60 minutes.

Certain embodiments of the present disclosure use a primary liquidprecursor and a secondary liquid precursor that are solids-free tocreate in-situ spherical beads in the fractures under hydraulic pressurewithin a reservoir and support the fracture to increase the permeabilityof the reservoir. The in-situ spherical beads replace traditionalproppants by being operable to keep the fractures open after thehydraulic fracturing and allow one or both of oil and gas to flowthrough the spaces between each bead. The present disclosure minimizesthe water needed for the hydraulic fracturing and the disposal of theflow back water after fracturing. The disclosure also eliminates theneed for solid proppants, polymers, breakers and other additivescommonly employed during conventional hydraulic fracturing.

One embodiment of the disclosure is the in-situ formation of in-situspherical beads from spherical bead-forming liquid composition, wherethe spherical bead-forming liquid composition was used as the hydraulicfracturing fluid to fracture the hydrocarbon containing reservoir andimprove the recovery of hydrocarbons. In at least one embodiment, thesecondary liquid precursor can be added simultaneously along with theprimary liquid precursor. In at least one embodiment of the disclosure,the secondary liquid precursor can be added sequentially after theprimary liquid precursor has been added to the reservoir through variousmechanical means known in the art.

The spherical bead-forming liquid composition reacts after placement inthe reservoir to form the in-situ spherical beads. Each of thecomponents described as present in the primary liquid precursor andsecondary liquid precursor can be added separately, but it is preferredfor handling and logistics purposes to divide the ingredients intoprimary liquid precursor and secondary liquid precursor and introducethese mixtures to the reservoir in the field in the form of thespherical bead-forming liquid composition.

The time required for the in-situ spherical beads to form, also referredto as the pot life, the size of the in-situ spherical beads, thedistribution of sizes, and the strength of the in-situ spherical beadscan be controlled by the composition of the primary liquid precursor andsecondary liquid precursor, such as the type and concentration of themicellar forming surfactant, the liquid non-solids bearing solvent, thebead-forming compound, the mono, di and poly cations dissolved in theliquid non-solids bearing solvent, the ratio of the primary liquidprecursor and secondary liquid precursor, the shear energy, thetemperature, the pressure, the reservoir environment and the pH.

Spherical beads can be generated having a diameter in the range fromabout 0.1 millimeters (mm) to about 30 mm, alternately in the range fromabout 0.1 mm to about 1 mm, alternately in the range from about 1 mm toabout 10 mm, alternately in the range from about 10 mm to about 15 mm,alternately in the range from about 15 mm to about 20 mm, alternately inthe range from about 20 mm to about 25 mm, and alternately from about 25mm to about 30 mm. In at least one embodiment of the disclosure, thesize of the in-situ spherical beads is affected by the composition ofthe spherical bead-forming liquid composition. In at least oneembodiment of the disclosure, the rheology of the spherical bead-formingliquid composition can be fine-tuned based on the components of theprimary liquid precursor and the secondary liquid precursor. FIG. 1shows the progress of spherical bead formation with time and FIG. 4shows the final spherical beads that can be made by varying the primaryliquid precursor and secondary liquid precursor.

Referring now to FIG. 4, the physical chemistry of the bead formingprocess leads to good sphericity of the beads. The good sphericity andlarge particle size help render highly uniform packing in the fractureto allow for the greatest fracture conductivity. FIG. 4 shows thesphericity of the in-situ formed proppant beads.

In an alternate embodiment, the in-situ spherical beads can be used tomodify the permeability of the reservoir formation and allow for spacesbetween each in-situ spherical bead for fluid to flow. Because thein-situ spherical beads are spherical or substantially spherical inshape and in size, they will pack in the fracture to allow for thegreatest amount of porosity between the beads. This is in contrast toconventional particles of irregular shapes and wide distribution in sizethat will pack much more tightly yielding lower permeabilities.Embodiments are designed to give in-situ spherical beads that are strongenough to withstand overburden pressure and prop open fractures formedduring hydraulic fracturing and acidizing.

In another embodiment, processes and compositions can be fine-tuned toalter the surface properties of the beads to encourage the flowproperties of the oil and gas in the reservoir. In some embodiments, thespherical beads are substantially uniform in size and shape. In someembodiments, the beads are substantially different in size and shape.

In another embodiment, the spherical beads can be used to consolidateand contain the unconsolidated sand in the near wellbore area.

In at least one embodiment, the spherical bead-forming liquidcomposition is in the absence of solid nucleating agent to generate thespherical beads. In at least one embodiment, only free-flowing,non-abrasive liquid is introduced into the reservoir avoiding abrasionto the pumping equipment.

In at least one embodiment, the spherical bead-forming liquidcomposition is in the absence of conventional fracturing fluidadditives. Exemplary conventional fracturing fluid additives includepolymers, cross-linkers, fluid loss additives, flow back additives, claystabilizers, corrosion inhibitors, scale inhibitors, biocides, flow backadditives, solid proppants, and gel breakers.

Referring to one embodiment, the primary liquid precursor is in theabsence of solids, and the secondary liquid precursor is in the absenceof solids. Therefore, the spherical bead-forming liquid composition isin the absence of solids. Exemplary solids include sand, resin coatedsand, pre-formed particles, filler, silica, silicate, silicon carbide,nano particles, fumed silica, carbon black, and combinations thereof. Inat least one embodiment, the spherical bead-forming liquid compositionis in the absence of proppant injected from the surface. The sphericalbead-forming liquid composition is in the absence of filler material.The in-situ spherical beads form in the absence of a template. As used,“template” refers to a material used to initiate the in-situ bead and onwhich the bead is allowed to build. Exemplary templates include carbonblack, fly ash, fumed silica, microspheres, silicon carbide, and thelike. The absence of solids in the spherical bead-forming liquidcomposition injected through a pump into the reservoir means minimalabrasion on the pumping equipment in contrast to conventional hydraulicfracturing fluids.

Current hydraulic fracturing processes in sandstone and shale formationsrequire injecting solid proppants to keep the induced fracturesconductive for hydrocarbon production. Injecting solid proppantspresents several challenges and disadvantages. Solid proppant density ismuch higher than that of the carrying fluid, therefore the proppantstend to settle to the bottom of the well or fractures. Fluids of highviscosity are often required, and they need to be injected at a veryhigh rate. In a complex fracture network, such as those developed inbrittle shale rocks, the solids may not effectively turn the corner atthe junction of the intersecting fractures. This limits the transporteddistance in the branch fractures, and is even likely to bridge off atthese intersections leaving only the main planar fracture propped. Theextensive network of induced fractures could close resulting in reduceddeliverability of the fractured network.

Conventional proppants must remain suspended while the fracture is beingpropagated and until the fracture is closed. Highly viscous gel isneeded to accomplish such an objective. These polymer-based gels couldleave residue to reduce the proppant pack conductivity and near fractureface permeability. Certain embodiments of the present disclosure do notrequire highly viscous gels. Proppants of very light density have beendeveloped to be able to allow using less viscous carrying fluids forefficiently transporting the proppants and minimize the gel damage. Butthe low density proppants naturally have lower strength and thereforecannot be used in deep and high stress reservoirs. Proppants areabrasive to pumping equipment and other tubes and piping, as theproppants are predominately silica, ceramic, or other hard solids.

The methods and compositions advantageously use less water to fracture areservoir than a conventional hydraulic fracturing fluid. In at leastone embodiment, the spherical bead-forming liquid composition uses about95% less water than a conventional hydraulic fracturing fluid. Thereduced water leads to reduced clay swelling and fluid imbibition inreservoirs with clay compositions.

In at least one embodiment, fluid leak off of the spherical bead-formingliquid composition is encouraged, as the spherical bead-forming liquidcomposition forms in-situ spherical beads in the micro-fractures, whichresults in an increase in permeability and an increase in theeffectiveness of the fracturing treatment.

In at least one embodiment, the fluid injected into the reservoir as thespherical bead-forming liquid composition reacts to form the in-situspherical beads, in which all or substantially all of the sphericalbead-forming liquid composition reacts leaving no fluid to flow back aswaste water that requires disposal.

The spherical bead-forming liquid composition can penetrate deeply intothe fractures produced in the reservoir formation, includingmicrofractures, thus producing in-situ spherical beads in even thesmallest fractures. The ability to penetrate fractures andmicrofractures generated in the reservoir formation can be attributed,in part, to the absence of solids in the spherical bead-forming liquidcomposition, as solids are known to block microfractures or anyfractures larger than the diameter of the solid. The deep penetration ofthe spherical bead-forming liquid composition into the fractures andsubsequent production of in-situ spherical beads generates flow channelsto increase the hydrocarbon production.

The spherical bead-forming liquid composition can be injected into awellbore in a reservoir formation to form in-situ spherical beads aspart of oil field applications to increase recovery of hydrocarbons.Exemplary oil field applications include hydrocarbon recovery,fracturing, water shut off, drilling, cementing, acidizing, sandconsolidation, permeability modification, water-flooding, chemicalenhanced oil recovery (CEOR), polymer flooding, and CO₂ flooding.

Unexpectedly, the proper choice of micellar forming surfactants, liquidsolvent carrier, pH, epoxy, curing agent, hardener, and co-curing agent,results in the formation of spherical beads within the formation. Thesespherical beads are effective in controlling fracture closure and,therefore, permeability due to their spherical shape, as shown in FIG. 1compared to proppants of irregular particles or porous solid blocks.

EXAMPLES Example 1

The primary liquid spherical precursor and secondary liquid precursor asshown in Table 1 were mixed for 10 minutes using a hand-mixer to form aspherical bead-forming liquid composition and then allowed to standundisturbed at 25° C. for 6 hours in a 50 ml centrifuge tube. Thein-situ spherical beads form as shown in FIG. 2. The strength of thespherical beads was tested using an Arbor 2-ton press and they held up apressure greater than 1,000 lb.

TABLE 1 Spherical bead-forming formation using an amphoteric surfactant.Primary liquid precursor Secondary liquid precursor Component Wt. %Component Wt. % Super Surfactant ® 6- 5.85 Adogen ™ AL42-12 14.6 72Alkylene amido propyl Fatty acid imidazoline dimethyl betaine 10% w/waqueous NaCl 51.2 Isophorone diamine 1.8 Bis-phenol A epoxy 21.9 50% w/waqueous NaOH 4.4 NoFoam ™ 1976 0.1 Note: Super Surfactant ® 6-72 is atrademark of Oil Chem Technologies, Inc. Adogen ™ is a trademark ofEvonik Industries. NoFoam ™ is a trademark of Oil Chem Technologies,Inc. Per Oil Chem Technologies, Inc. NOFOAM ™ 1976 ™ is a silicone freeanti-foam agent, combining properties of organosilicone and organicbased foam control agents. It is stable in extreme pH ranges (pH <1-14)and it is stable at temperatures greater than 350° F.

Example 2

The primary liquid precursor and secondary liquid precursor formulatedaccording to the composition as shown in Table 2 were mixed for 30minutes, then allowed to stand undisturbed at 60° C. for 6 hours in acapped 4 ounce jar. The spherical beads formed as shown in FIG. 3. Thestrength of the spherical beads was tested using the Arbor 2-ton pressand they held up a pressure greater than 1,200 lb.

TABLE 2 In-situ spherical bead composition using NaCl solution and ananionic surfactant. Primary liquid precursor Secondary liquid precursorComponent Wt. % Component Wt. % Sodium C14-16 alpha- 10.7 Ancamine ™ TPolyamine 21.5 olefin sulfonate adduct 10% w/w aqueous NaCl 21.5 2-ethylhexanol 10.7 Bis-phenol F epoxy 32.2 50% w/w aqueous NaOH 3.2 NoFoam ™1976 0.2 Note: Ancamine ™ is a trademark of Air Products Inc. Ancamine Tcuring agent (2-hydroxy ethyl) diethylene triamine (technical grade) isan ambient or elevated temperature curing agent for use with liquidepoxy resins.

Example 3

The primary liquid precursor and secondary liquid precursor according tothe composition as shown in Table 3 were mixed for 30 minutes to formthe spherical bead-forming liquid composition and then allowed to standundisturbed at 60° C. to react and form the in-situ spherical beads. Thestrength of the spherical beads was tested using the Arbor 2-ton pressand they held up a pressure greater than 1,200 lb. The beads formed areshown in FIG. 4.

Example 3: In-situ spherical bead composition in sea water usingcationic surfactant.

Primary liquid Secondary precursor liquid precursor Component Wt. %Component Wt. % Hyamine ® 1622 7.9 Max CLR ™ B 30.7 Sea water 30.7 MaxCLR ™ A 30.7 Note: Hyamine ™ is a registered trademark of LonzaCorporation. Hyamine ™ 1622 is a cationic detergent benzethoniumchloride, also called (Diisobutylphenoxyethoxyethyl)dimethylbenzylammonium chloride solution. Max CLR ™ is a trademark ofPolymer Composites Corporation. Max CLR ™ A is a modified bisphenol Aepoxy resin, 90-100% by weight phenol, 4-(1-methylethylidene) Bis,Polymer with (Chloromethane) Oxerane, 1-5% by weight epoxidize diluentreactive, 0-10% by weight epoxidize cresylglyciderether modified, and0.1-0.5% by weight non-silicone additive. Max CLR ™ B is an aminemodified curing agent. It contains about between 5-15% by weight benzylalcohol, 15-35% by weight isophoronediamine adduct, and 50-60% by weightaliphatic amine adduct.

Example 4

The primary liquid precursor was mixed with the secondary liquidprecursor for 30 minutes to form the spherical bead-forming liquidcomposition. The spherical bead-forming liquid composition was then heldat 60° C. for 10 hours and as a result formed black-colored sphericalbeads as shown in FIG. 5. The strength of the spherical beads was testedusing the Arbor 2-ton press. The spherical bead strength held up to apressure greater than 1,000 lb.

TABLE 4 In-situ spherical bead formation composition using crude oil assolvent. Primary liquid precursor Secondary liquid precursor ComponentWt. % Component Wt. % Super Surfactant ® 6-72 8.6 Mackazoline ™ T 10.8Fatty acid imidazoline complex salt 10% w/w aqueous NaCl 10.8 Isophoronediamine 0.6 50% w/w aqueous NaOH 6.5 Benzyl alcohol 4.3 Crude oil, APIgravity = 29 21.6 Bisphenol F Epoxy resin 36.6 Note: Makazoline ™ is atrademark of Solvay. Per Solvay, Makazoline ™ is Fatty amine which, whenneutralized with common acids, acts as a cationic surface active agentand emulsifier. It is oil soluble and water dispersible and contains nosolvents. A synonym is tall oil hydroxyethyl imidazoline.

Example 5

The primary liquid precursor and secondary liquid precursor are mixedcontinuously in a stainless steel beaker using a mechanical stirrer withthe rheostat speed set at 5 and allowed to react. The stainless steelbeaker is set in a water bath to maintain the reaction temperature at60° C. During the reaction, samples were collected in 60 minuteintervals and placed in a 60° C. oven un-disturbed for 4 hours toevaluate the size of the spherical beads formed. The test showed thatthe size of the spherical beads got smaller with increased mixing time,as shown in the graph of the diameter of the spherical beads versus thepot life in FIG. 6.

The diameter of the spherical beads ranged from 0.5 mm to 12 mm due tothe shear energy and the mixing time. The size of the spherical beadscan be correlated to the residence time of the spherical bead-formingliquid composition in the fracturing process where the fluids in thefracture front experience the longest pumping time and form smallerbeads at the tip of the fractures and in the micro-fractures, whereasthe fluids closer to the well bore form larger beads. FIG. 7 shows thelikely size of the spherical beads formed in the fractures in oneembodiment. The pot life is the time prior to bead formation andcorrelates to the distance the fracturing fluid travels through thereservoir before the pumping in stopped.

TABLE 5 Selective fracture packing by pot life control. Primary liquidprecursor Secondary liquid precursor Component Wt. % Component Wt. %Super Surfactant ™ 6-72 7.1 Tall Oil Fatty Acid 28.3 Alkylene dimethylImidazoline amido betaine 10% w/w aqueous NaCl solution 28.3 Diethylenetriamine 0.7 50% w/w aqueous NaOH 7.2 Bisphenol F Epoxy 28.3 NoFoam ™1976 0.1

Example 6

In this example a glass column was prepared containing spherical beadsformed using the method described in Example 1 (Example 1 beads). Asecond column was prepared using 40-60 mesh sand. A crude oil of APIgravity 29 was poured into each tube, and the rate at which the oilflowed through the columns was observed and compared.

FIG. 8 shows the pictures taken before and at 5 minutes after the oilwas added. The oil flow through the column with Example 1 beads (left)was faster than the flow of oil through the column with sand (right),illustrating the effectiveness of the beads as a proppant compared tothe sand. Without being bound to a particular theory, it is believedthat the use of fracturing sand as a proppant is limited because if itis too large it will settle out before propagating deep into thefracture. Alternately, it may plug the pumping equipment. The sphericalbeads that are larger than the sand create larger spaces between theindividual beads and thus greater permeability.

Referring now to FIG. 9, a pictorial representation is shown of avariety of sizes of solid beads produced under an in-situ temperature of150° F. The formation of similar beads is shown in FIG. 1 as well. Thespherical beads are strong enough to withstand overburden pressure andprop open fractures formed during hydraulic fracturing and acidizing.

Referring now to FIG. 10, a schematic representation is shown of amechanical load-bearing test performed on spherical beads produced byembodiments of the present disclosure. Mechanical property tests areconducted by using a hydraulic press 1000 with a load cell 1002 and apiston 1004 to apply a load 1006 on a 1 inch diameter by 1 inch thickproppant pack 1008 at ambient temperature. The stress is slowly appliedto the cylindrical pack at a constant displacement speed (0.5 mm/min)until the stress reaches 14,000 psi. The stress vs. strain curve isconstructed to analyze the mechanical behavior and strength of thepacked material. FIG. 10 illustrates the load cell assembly with theproppant pack.

The piston is set to continuously move down at a constant speed of 0.5mm/min while the resultant load due to the proppant pack resisting thechange in thickness is measured by a transducer on the hydraulic frameof an Instron Model 3069. Comparison between the in-situ proppant andconventional proppants, including 16/30 intermediate strength proppants(ISP), 16/20 resin coated proppants (RCP), 20/40 light weight ceramicproppants (LWCP), and high strength bauxite proppants (HSP), are made.

Referring now to FIG. 11, a graph is shown comparing the mechanicalbehavior among two in-situ proppant formulations of the presentdisclosure, conventional high strength bauxite proppant (20/40 HSP), andintermediate strength proppant (16/30 ISP). FIG. 11 shows the stress vs.strain curve for the mechanical behavior comparison between the in-situproppants, intermediate strength proppant (ISP), and high strengthbauxite proppant (HSP) packs. Two chemical formulations of the in-situproppants are tested. Both in-situ proppants show highly flexible andelastic characteristics in the low stress regime.

As the stress increases, the proppant packs become much stiffer whileremaining highly elastic. Loading the proppant packs to 14,000 psi doesnot result in any crushing. The grain shapes remain nearly the same asindicated by the photo in FIG. 12 for in-situ proppant-1. The bulkdensity of the in-situ proppant pack is approximately 0.68, and thegrain apparent density is 1.05. The porosity of the initial proppantpack is approximately 35%. There is a thickness reduction experienced bythe in-situ proppant pack under 14,000 psi stress.

The stress-strain curves for the two in-situ proppants show reduction ofpack thickness by 30% before pressure is applied (in-situ proppant-2)and 50% after 14,000 lbs/in² pressure is applied (in-situ proppant-2).These stains translate to losses of porosity by the same levels.

Since the proppant diameter of the spherical beads is significantlylarger than the diameter of conventional proppant particulates, theinitial conductivity will be significantly higher than it is withconventional proppants. Along with the zero fines generation, theconductivity is expected to be sufficient over time.

Referring now to FIG. 12, a pictorial representation is shown of thespherical particles of the in-situ proppant 1 pack from FIG. 11rebounded to nearly the same shape, as stress is released from themaximum loading of 14,000 psi. Conventional brittle HSP shows highstiffness throughout the loading process, however the stress-straincurve shows very minor elastic modulus reduction when loaded to greaterthan 10,000 psi. ISP pack starts to deviate from the linear elasticityat 8,000 psi. These are the stresses at which the onset of graincrushing is initiated.

FIG. 13 shows a few crushed grains after the HSP is loaded to 14,000psi, whereas FIG. 14 shows a significant fines content is generated whenthe ISP is loaded to 14,000 psi. FIG. 13 is a pictorial representationshowing grains of the 20/40 HSP from FIG. 11 before (left) and after(right) being loaded to 14,000 psi. FIG. 14 is a pictorialrepresentation of the grains of the 16/30 ISP from FIG. 11 before (left)and after (right) being loaded to 14,000 psi. Significant grain crushingand fines generation is observed.

FIG. 15 is a pictorial representation of grains of 16/20 resin coatedproppant (RCP) before (left) and after (right) being loaded to 14,000psi. Significant grain crushing and fines generation is observed.

FIG. 16 is a pictorial representation of grains of 20/40 light weightceramic proppant (RCP) before (left) and after (right) being loaded to14,000 psi. Significant grain crushing and fines generation is observed.

Although the disclosure has been described with respect to certainfeatures, it should be understood that the features and embodiments ofthe features can be combined with other features and embodiments ofthose features.

Although the disclosure has been described in detail, it should beunderstood that various changes, substitutions, and alterations can bemade hereupon without departing from the principle and scope of thedisclosure. Accordingly, the scope of the present disclosure should bedetermined by the following claims and their appropriate legalequivalents.

The singular forms “a,” “an,” and “the” include plural referents, unlessthe context clearly dictates otherwise.

Optional or optionally means that the subsequently described event orcircumstances can or may not occur. The description includes instanceswhere the event or circumstance occurs and instances where it does notoccur.

Ranges may be expressed throughout as from about one particular value,and to about another particular value. When such a range is expressed,it is to be understood that another embodiment is from the oneparticular value and to the other particular value, along with allcombinations within said range.

As used throughout the disclosure and in the appended claims, the words“comprise,” “has,” and “include” and all grammatical variations thereofare each intended to have an open, non-limiting meaning that does notexclude additional elements or steps.

As used throughout the disclosure, terms such as “first” and “second”are arbitrarily assigned and are merely intended to differentiatebetween two or more components of an apparatus. It is to be understoodthat the words “first” and “second” serve no other purpose and are notpart of the name or description of the component, nor do theynecessarily define a relative location or position of the component.Furthermore, it is to be understood that that the mere use of the term“first” and “second” does not require that there be any “third”component, although that possibility is contemplated under the scope ofthe present disclosure.

While the disclosure has been described in conjunction with specificembodiments thereof, it is evident that many alternatives,modifications, and variations will be apparent to those skilled in theart in light of the foregoing description. Accordingly, it is intendedto embrace all such alternatives, modifications, and variations as fallwithin the spirit and broad scope of the appended claims. The presentdisclosure may suitably comprise, consist or consist essentially of theelements disclosed and may be practiced in the absence of an element notdisclosed.

What is claimed is:
 1. A hydraulic fracturing fluid for use in oilfieldapplications, the hydraulic fracturing fluid comprising: a sphericalbead-forming liquid composition, the spherical bead-forming liquidcomposition comprised of a primary liquid precursor and a secondaryliquid precursor, the primary liquid precursor comprises: a micellarforming surfactant, a bead-forming compound, and a non-solids bearingliquid solvent; and the secondary liquid precursor comprises: a curingagent, and a co-curing agent.
 2. The composition of claim 1, where theprimary liquid precursor further comprises an anti-foaming agent.
 3. Thecomposition of claim 1, where the primary liquid precursor furthercomprises a pH control agent.
 4. The composition of claim 1, where themicellar forming surfactant is selected from the group consisting ofanionic surfactants, cationic surfactants, nonionic surfactants,amphoteric surfactants and combinations thereof.
 5. The composition ofclaim 1, where the bead-forming compound is selected from the groupconsisting of bis-phenol A, bis-phenol F, cycloaliphatic epoxides,glycidyl ethers, poly glycidyl ethers, novalac resins, polyurethaneresins, acrylic resin, phenol-formaldehyde resin, epoxy functionalresins, and combinations thereof.
 6. The composition of claim 1, wherethe non-solids bearing liquid solvent is selected from the groupconsisting of water, brine containing mono and polyvalent salt, seawater, mineral oil, kerosene, diesel, crude oil, and petroleumcondensate, low molecular weight alcohols, low molecular weight alcoholethers, benzyl alcohol, and benzyl alcohol ethers, ethyl carbitol ether,γ-butyrolactone, phenol alkoxylates, alkylphenol alkoxylates, andcombinations thereof.
 7. The composition of claim 3, where the pHcontrol agent is selected from the group consisting of hydrochloricacid, sulfuric acid, phosphoric acid, sodium hydroxide, potassiumhydroxide, sodium carbonate, sodium aluminate, potassium carbonate,potassium phosphate, sodium silicate, potassium silicate, organic acids,and combinations thereof.
 8. The composition of claim 1, where thecuring agent is selected from the group consisting of lewis acids,tertiary amines, mono ethanol amine, benzyl dimethylamine,1,4-diaza-bicylo[2,2,2]octane, 1,8-diazabicylo[5,4,0]undec-7ene,cycloaliphatic amines, amidoamines, aliphatic amines, aromatic amines,isophorone, isophorone diamine, polyamides, boron tri-fluoridederivatives, functional resins, imidazoles, imidazolines, mercaptans,sulfide, hydrazides, amides and their derivatives.
 9. The composition ofclaim 1, where the co-curing agent is selected from the group consistingof water, fatty acids, such as oleic acid, tall oil fatty acid,ricinoleic acid, benzoic acid, salicylic acid, stearic acid as well asalkoxylated alcohols, dicarboxylic acids, carboxylic acids,imidazolines, dicyandiamides, ureas, imidazoles, thiols, aliphaticpolyamines, cycloaliphatic polyamides, cycloaliphatic dicarboxylic acidanhydrides, imidazoline salts, dicyandamides, phenols and alkylphenols.10. The composition of claim 1, where the spherical bead-forming liquidcomposition is a non-solids bearing homogenous liquid.
 11. Thecomposition of claim 1, where the spherical bead-forming liquidcomposition has a liquid viscosity from about 20 centipoise (cp) toabout 80 cp.
 12. A method of fracturing a reservoir with a sphericalbead-forming liquid composition that forms a hydraulic fracturing fluidthat generates fractures in the reservoir, the method comprising thesteps of: mixing a primary liquid precursor and a secondary liquidprecursor to form the spherical bead-forming liquid composition, wherethe primary liquid precursor comprises: a micellar forming surfactant, abead-forming compound, and a non-solids bearing liquid solvent; wherethe secondary liquid precursor comprises: one or more curing agents, andone or more co-curing agents; pumping the spherical bead-forming liquidcomposition into an injection well in the reservoir at an externalpressure greater than a pressure to generate fractures in the reservoir;allowing the spherical bead-forming liquid composition to migrate intothe fractures of the reservoir; and allowing the primary liquidprecursor and secondary liquid precursor to react to form in-situspherical beads, the in-situ spherical beads are operable to keep thefractures open after the external pressure is released.
 13. The methodof claim 12, further comprising the step of adding an anti-foaming agentto the primary liquid precursor.
 14. The method of claim 12, furthercomprising the step of adding a pH control agent to the primary liquidprecursor.
 15. The method of claim 12, where the micellar formingsurfactant is selected from the group consisting of anionic surfactants,cationic surfactants, nonionic surfactants, amphoteric surfactants andcombinations thereof.
 16. The method of claim 12, where the bead-formingcompound is selected from the group consisting of bis-phenol A,bis-phenol F, cycloaliphatic epoxides, glycidyl ethers, poly glycidylethers, novalac resins, polyurethane resins, acrylic resin,phenol-formaldehyde resin, epoxy functional resins, and combinationsthereof.
 17. The method of claim 12, where the non-solids bearing liquidsolvent is selected from the group consisting of water, brine containingmono and polyvalent salt, sea water, mineral oil, kerosene, diesel,crude oil, and petroleum condensate, low molecular weight alcohols, lowmolecular weight alcohol ethers, benzyl alcohol, and benzyl alcoholethers, ethyl carbitol ether, γ-butyrolactone, phenol alkoxylates,alkylphenol alkoxylates, and combinations thereof.
 18. The method ofclaim 14, where the pH control agent is selected from the groupconsisting of hydrochloric acid, sulfuric acid, phosphoric acid, sodiumhydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,potassium phosphate, sodium silicate, potassium silicate, organic acids,and combinations thereof.
 19. The method of claim 12, where the one ormore curing agents are selected from the group consisting of lewisacids, tertiary amines, mono ethanol amine, benzyl dimethylamine,1,4-diaza-bicylo[2,2,2]octane, 1,8-diazabicylo[5,4,0]undec-7ene,cycloaliphatic amines, amidoamines, aliphatic amines, aromatic amines,isophorone, isophorone diamine, polyamides, boron tri-fluoridederivatives, functional resins, imidazoles, imidazolines, mercaptans,sulfide, hydrazides, amides and their derivatives.
 20. The method ofclaim 12, where the one or more co-curing agents are selected from thegroup consisting of water, fatty acids, such as oleic acid, tall oilfatty acid, ricinoleic acid, benzoic acid, salicylic acid, stearic acidas well as alkoxylated alcohols, dicarboxylic acids, carboxylic acids,imidazolines, dicyandiamides, ureas, imidazoles, thiols, aliphaticpolyamines, cycloaliphatic polyamides, cycloaliphatic dicarboxylic acidanhydrides, imidazoline salts, dicyandamides, phenols and alkylphenols.21. The method of claim 12, where the spherical bead-forming liquidcomposition is a non-solids bearing homogenous liquid.
 22. The method ofclaim 12, where the spherical bead-forming liquid composition has aliquid viscosity from about 20 centipoise (cp) to about 80 cp.